An agricultural composition which comprises as an active ingredient at least one of the 3,5-dichlorophenyl compounds represented by either one of the following formulae:...http://www.google.com/patents/US3925554?utm_source=gb-gplus-sharePatent US3925554 - Certain 3,5-dichlorophenyl compound used as a plant fungicide

[57] ABSTRACT An agricultural composition which comprises as an ac- Dec. 9, 1975 live ingredient at least one of the 3,5-dichlorophenyl compounds represented by either one of the following formulae:

- coon C1 appreciable toxicity to crop plants or to mammals and fish.

and

16 Claims, N0 Drawings CERTAIN 3,5-DICHLOROPHENYL COMPOUND USED AS A PLANT FUNGICIDE The present invention relates to an agricultural composition. More particularly, it relates to an agricultural composition comprising as an active ingredient at least one of the 3,5-dichlorophenyl compounds represented by either one of the following formulae:

wherein A is a methylene group or an oxygen atom in Formula I but only a methylene group in Formula II and R is a hydrogen atom or an alkali metal atom (e.g. sodium, potassium), which exhibits a remarkable antifungal activity against phytopathogenic fungi without any appreciable toxicity to crop plants or to mammals and fish.

in the 3,5-dichlorophenol compounds represented by the formula [I] or [II], there are included the following three kinds of compounds:

Compound (ll-A) N-( 3 ',5 '-Dichlorophenyl )-norbornane-2,3-dicarboximide These 3,5-dichlorophenyl compounds are known and described to be useful as veterinary medicaments (cf. US. Pat. Nos. 3,215,597 and 3,261,845]. Further, it is described that N-4-fluorophenyl-3,o-epoxyhexahydrophthalimide which does not fall within the compounds of the formulae [1] and [ll] but is similar thereto in chemical structure has an acaricidal activity [cf. US. Pat. No. 3,26l,845]. However, no literature has ever suggested the practical use of the 3,5- dichlorophenyl compounds [I] and [ll] as an active ingredient in an agricultural composition, particularly in fungicidal compositions against phyto-pathogenic fungi.

As the result of extensive studies, it has now been found that the 3,5-dichlorophenyl compounds [I] and [I1 possess an unexpectedly high anti-fungal activity against phyto-pathogenic fungi including Sclerotinia scleroliorum, Rhizoctom'a solani, Botrytis cinerea, Piricularia oryzae, Cochliobolus miyabeanus, Pellicularr'a sasakii, etc. It has also been found that the 3,5- dichlorophenyl compounds [I] and [ll] do not cause any phytotoxicity on crop plants when applied in an amount which is sufficient to exert an anti-fungal activity. It has further been found that the 3,5-dichlorophenyl compounds [I] and [II] exhibit an extremely low toxicity with regard to mammals and fish.

in this connection, it should be noted that a number of compounds closely related to the 3,5-dichlorophenyl compounds [I] and [ll] in chemical structure have been known but their anti-fungal activity is so weak as to preclude any practical application.

Typical examples of the agricultural composition according to this invention are:

a. Dusts obtained by dispersing at least one of the 3,5-dichloropheny compounds [l]l]and [II] as the active ingredient in a concentration of 0.1 to 30 by weight in an inert carrier (e.g. talc, diatomaceous earth, wood flour, clay).

b. Wettable powders obtained by dispersing at least one of the 3,5-dichlorophenyl compounds [I and [ll] as the active ingredient in a concentration of 0.2 to by weight in an inert adsorbent carrier (e.g. diatomaceous earth) together with a wetting and/or dispersing agent such as an alkali metal salt of a long aliphatic sulfate chain, a partly neutralized sulfuric acid derivative of either a petroleum oil or a natural occurring glycerine or a condensation product of an alkylene oxide with an organic acid.

c. Emulsifiable concentrates obtained by dispersing at least one of the 3,5-dichlorophenyl compounds [I] and [ll] as the active ingredient in a concentration of l to 50 by weight in an organic solvent (e.g. dimethylsulfoxide) plus a wetting and/or dispersing agent such as an alkali metal salt of a long aliphatic sulfate chain, a partly neutralized sulfuric acid derivative of either a petroleum oil or a natural occurring glycerine or a condensation product of an alkylene oxide with an organic acid.

d. Compositions of the 3,5-dichlorophenyl compounds [I] and [ll] formulated in the manner commonly employed in the art for the preparation of fungicidal fumigants.

More specific examples of the agricultural composition of this invention are shown below. In these examples, parts and are by weight.

EXAMPLE 1 Preparation of wettable powders:

A. Compound (ll-A), i.e. N-(3',5-dichlorophenyl)- norbornane-2,3-dicarboximide (M.P. l7l.0172.5C), (50 parts), a wetting agent (an alkylbenzenesulfonate) (5 parts) and diatomaceous earth (45 parts) are crushed and mixed well to form a wettable powder preparation containing 50 of the active ingredient. The wettable powder preparation is diluted with water and then applied.

A. Compound (LA: R=H), i.e. 3-(3',5'-dichlorophenylcarbamoyl)-norbornane-2-carboxylic acid (M.P. I5l.5l53.5C), (3 parts) and clay (97 parts) are crushed and mixed well to form a dust preparation containing 3 of the active ingredient. The dust preparation is applicable as such.

B. Compound (l-B: R=H), i.e. 3-(3',5-dichlorophenylcarbamoyl )-7-oxabicyclo(2,2,l )heptane-Z-carboxylic acid (M.P. l83l84C), is used in place of Compound (l-A: R=H) for the formulation of a dust preparation as in Example 2 (A).

EXAMPLE 3 Preparation of emulsifiable concentrates:

A. Compound (ll-A) parts). dimethylformamide (70 parts), toluene (10 parts) and an emulsifier (polyoxyethylenedodecylphenol ether) (10 parts) are mixed well to form an emulsifiable concentrate preparation containing 10 of the active ingredient. The emulsifiable concentrate preparation is diluted with water and then applied.

B. Compound (l-B: R=H) is used in place of Compound (ll-A) forthe formulation of an emulsiiiable concentrate preparation as in Example 3 (A).

EXAMPLE 4 Preparation of fumigants:

A. Compound (ll-A) (90 parts), a nitrite (3 parts), wood flour (2 parts) and diatomaceous earth (5 parts) are pulverized and mixed well to form a fumigant preparation containing 90 of the active ingredient. The fumigant preparation is applied by fumigating on a heating fumigator.

B. Compound (l-B: R=H) is used in place of Compound (ll-A) for the formulation of a fumigant preparation as in Example 4 (A).

EXAMPLE 5 Preparation of complex wettable powders:

A. Compound (ll-A) parts), S-n-butyl-S'-(p-tbutylbenzyl)-N-( B-pyridyl)-dithiocarbonate l0 parts), diatomaceous earth parts) and a wetting agent (calcium ligninsulfonate) (5 parts) are pulverized and mixed well to form a complex wettable powder preparation containing of the active ingredients. The complex wettable powder preparation is diluted with water and then applied.

B. Compounds (l-B: R=H) (4 parts), manganese ethyienebis(thiocarbamate) parts), diatomaceous earth (30 parts) and a wetting agent (an alkylbenzenesulfonate) (6 parts) are pulverized and mixed well to form a complex powder preparation containing 64 of the active ingredients. The complex wettable powder preparation is diluted with water and then applied.

C. Compound (l-A: R=H) is used in place of Compound (LB: R=H) for the formulation of a complex wettable powder preparation as in Example 5 (B).

Some of the test results which support the anti-fungal activity of the 3,5-dichlorophenyl compounds [I] and [ll] are shown below.

The known compounds used in the following tests for comparison are as follows:

Compound No. Structure Remarks 00" Cl c Disclosed in l US. Pat. No.

COOH

Disclosed in 2 U.S. Pat. No.

CON" c 3,215,597

(00H Disclosed in 3 U.S. Pat. No.

15, 97 ONH c1 3 2 5 c c Disclosed in 4 U.S. Pat. No.

Ci 3.25.597 CG coon I Disclosed In 5 U.S. Pat. No.

Disclosed in 6 N U.S. Pat. No.

Disclosed in 7 U.S. Pat. No.

3.25.597 CONH c1 TEST 1 Infection N umber index of stems Total number of stems X 3 100 Degree of infection wherein the infection index was determined on the following criteria:

Infection index Infectious state 0 No infectious spots on sheath 1 Infectious spot-like parts 2 Infectious spots of less than 3 cm in size 3 Infectious spots of not less than 3 cm in size The results are shown in Table 1, from which it is seen that the 3,5-dichlorophenyl compound (l-B: R=H) has a stronger anti-fungal activity than the analogous compounds such as the corresponding monochlorinated compounds.

A test compound in wettable powder form was diluted with water and applied to kidney bean seedlings cultured in pots of 9 cm in diameter and grown up to the two leaved stage at a dose of IO ml of the dilution per pot. After 4 hours, a mycelium-disc-inoculum of Sclerotinia sclerotiorum (diameter, 5 mm) was inoculated on the leaves. The infectious area at the leaves was observed 4 days thereafter, and the degree of damage was calculated according to the following equation:

2 Infection X Number of D f index leaves agree 0 damage Total number of leaves wherein the infectious index was determined on the following criteria:

Infectious index Infectious area None Only around the inoculated parts Up to 1/5 of the total area of the inoculated leaf More than 1/5 and up to 2/5 of the total area of the inoculated leaf More than 2/5 and up to 3/5 of the total area of the inoculated leaf More than 3/5 of the total area of the inoculated leaf 8 The results are fslidvvn i ri Table 2, from which it is understood that the 3,5{dichlorophenyl compounds (I-A: R=H), (l-B: R=H), '(I-B: R =Na) and (II-A) have a stronger anti-fungal activity than the analogous compounds such as the corresponding monochlorinated compounds.

Trade name for a fungicidal composition comprising 2,fi-dichlonvknilroanilinc as the active ingredient.

TEST 3 Kidney bean seedlings cultured in pots of 9 cm in diameter and grown up to the first trifoliate stage (five pots per plot) were exposed to fumes of a test compound, said fumes being produced on a heating fumigator. Exposure was made for 15 hours in a space enclosed by vinyl sheets, and then the vinyl sheets were removed. Besides, the plants as above were subjected to foliage treatment with a 1000 fold dilution of a 30 wettable powder of the test compound at a dose of 100 liters of the dilution per 10 are. After seventeen hours from the treatments in both cases, a mycelium-diso inoculum of Sclerotinia scleroti'orum was inoculated on the surface and the reverse of the leaves. The infectious area at the leaves was observed 4 days thereafter, and the degree of damage was calculated according to the following equation:

Infection Number of 2 index X leaves Degree of damage Total number of leaves wherein the infectious index was determined on the following criteria:

The results are shown in Table 3, from which it can be understood that the 3,5-dichlorophenyl compounds (l-B: R=H) and (ll-A) exert an excellent anti-fungal activity not only when applied in a wettable powder form but also when applied in a fumigant form.

the leaf was trimmed. A test compound in wettable powder form was diluted with water and applied to the seed leaf of the plants at a dose of 10 ml of the dilution per pot. After four hours, a mycelium-disc-inoculum of Botryu's cinerea (diameter, 5 mm) was inoculated on the leaves. The infectious area at the leaves was observed 5 days thereafter, and the degree of damage was calculated as in Test 3.

The results are shown in Table 4, from which it is seen that the 3,5-dichlorophenyl compounds (l-A:

sowed therein. Five days thereafter, the infectious state of the grown seedlings was observed, and the percentage of stand was calculated according to the following equation:

TEST 5 compound in emulsifiable concentrate form was diluted with water to make a 500 ppm concentration, and the dilution was poured into the said pot at a rate of 15 ml per pot. After 4 hours, 20 seeds of radish were sowed therein. Three weeks thereafter, the infectious state of the grown seedlings was observed, and the percentage of stand was calculated as in Test 5.

The results are shown in Table 8, from which it is understood that the 3,5-dichlorophenyl compounds (I-B: R=H) and (1-8: R=Na) have a stronger anti-fungal activity than the analogous compounds such as the corresponding monochlorinated compounds.

As understood from the above test results, the 3,5- dichlorophenyl compounds [I] and [ll] are useful for the control and prevention of such plant diseases as Sclerotinia rot, Rhizoctonia rot and Botrytis gray mold of vegetables and field crops, and blast, brown leaf spot and sheath blight of rice plants.

The 3,5-dichlorophenyl compounds [I] and [ll] may be applied as such. From the practical viewpoint, however, they are usually employed in the form of compositons in association with any agricultural acceptable inert carrier or diluent as well as any surface active agent or wetting agent. The concentration thereof in the compositions may be from about 0.1 to 90 by weight, although such is not essential.

What is claimed is:

l. A methodfor killing phyto-pathogenic fungi on plants which comprises applying to said fungi a fungicidally effective amount of a 3,5-dichlorophenyl compound of the formula 2. The method according to claim 1, wherein the 3,5- dichlorophenyl compound is applied to said fungi in the form of a composition comprising said compound and an inert carrier.

3. The method according to claim 2, wherein the concentration of the 3,5-dichlorophenyl compound in said composition is 0.1 to 90% by weight.

4. A method for killing phyto-pathogenic fungi selected from the group consisting of the genera Sclerotinia and Botrytis on plants which comprises applying to said fungi a fungicidally effective amount of a 3,5- dichlorophenyl compound of the formula:

5. The method according to claim 4, wherein the 3,5-

dichlorophenyl compound is applied to said fungi in the 5 form of a composition comprising said compound and an inert carrier.

6. The method according to claim 4, wherein the phyto-pathogenic fungus is Sclerotinia sclerou'orum.

7. The method according to claim 4, wherein the phyto-pathogenic fungus is Botrytis cincrea.

8. A method for killing phyto-pathogenic fungi selected from the group consisting of 'Sclerotinia sclerotiorum, Rhizoctonia solam', Botrytis cinerea, Piricularia oryzae, Cochliobolus miyabeanus, Pellicularia sasakii, Pelliculan'a filamentosa, and Fusarium oxysporum F. raphani on plants which comprises applying to said fungi a fungicidally effective amount of a 3,5- dichlorophenyl compound of the formula:

9. The method according to claim 8, wherein the 3 ,5-

dichlorophenyl compound is applied to said fungi in the form of a composition comprising said compound and an inert carrier.

10. The method according to claim 8, wherein the concentration of the 3,5-dichlorophenyl compound in said composition is 0.1 to 90% by weight.

11. The method according to claim 8, wherein the phyto-pathogenic fungus is Rhizoctom'a solam'.

12. The method according to claim 8, wherein the phyto-pathogenic fungus is Pt'ricularia oryzae.

13. The method according to claim 8, wherein the phyto-pathogenic fungus is Cochli'obolus miyabeanus.

14. The method according to claim 8, wherein the phyto-pathogenic fungus is Pellicularia sasakii.

15. The method according to claim 8, wherein the ph toathogenic fungus is Pellicularia filamentosa.